Advances in the NMR Spectroscopy of Polymers: An Overview - ACS

Chapter 1

Advances in the NMR Spectroscopy of Polymers: An Overview 1

Downloaded by CORNELL UNIV on September 6, 2016 | http://pubs.acs.org Publication Date: December 10, 2002 | doi: 10.1021/bk-2003-0834.ch001

H . N . Cheng and Alan D . English

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Hercules Incorporated Research Center, 500 Hercules Road, Wilmington, DE 19808-1599 DuPont Central Research and Development, Experimental Station, Wilmington, DE 19880-0356

N M R spectroscopy is being used extensively to study both synthetic and natural polymers. Many techniques and methodologies have been developed, and these have been applied to a large number of polymeric systems. A n overview is provided here of the recent advances in this field, covering both liquid-state and solid-state N M R . For illustration, pertinent examples are taken from selected publications in the literature and from the papers included in this symposium volume.

NMR spectroscopy is a well-known and popular technique for polymer characterization. The literature on this topic is vast and continues to grow. For example, according to Chemical Abstracts the number of publications containing " N M R " and "polymer" as the key words has hovered around 600 per year in the last few years.

© 2003 American Chemical Society

Cheng and English; NMR Spectroscopy of Polymers in Solution and in the Solid State ACS Symposium Series; American Chemical Society: Washington, DC, 2002.

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In the past 4-5 years, quite a number of relevant review articles and books have appeared. These included general reviews on N M R of polymers (1-10), reviews on solid state N M R (11-15), solid state multidimensional techniques (16-19), spatially resolved techniques (20), solid state N M R studies of polymer dynamics and structure (21), hydrated polymers (22), vulcanized elastomers (23), crosslinked polymers (24), and polymer networks (25). Reviews have also been written on polymer gels (26-28), polymer colloids (29), polymer-surfactant systems (30), and polymers on surfaces (31). In liquid state N M R , other than the general reviews noted above, reviews have appeared on chemical shift calculations (32) and on computer-assisted approaches (33). In addition, the N M R of polypropylene (34) and dienes and polyenes (35) has been specifically reviewed. N M R imaging has been increasingly applied to polymeric materials. Several reviews have appeared (36-41). In this article, an overview is given of this field, with an emphasis on the development of new or improved techniques and methodologies. In order to narrow the scope, only solution and solid state N M R techniques are covered. The polymeric systems chosen as examples are taken from the literature and particularly from the papers included in this symposium volume (42-71). Also included are selected preprints taken from the papers presented at the international symposium on High Resolution N M R Spectroscopy of Polymers held at the A C S National Meeting in April, 2001 in San Diego, C A (72-87).

Solution N M R The use of solution N M R for polymer analysis has become routine in many laboratories. N M R is used to monitor the extent of a reaction, to check the purity of polymers, to identify unknown materials, and to study polymer


5 microstructure, dynamics, and interactions. Because of its wide usage, a large number of new or improved techniques and methodologies continue to appear. A summary of many of these developments is given below.


1.

Multidimensional NMR

Since its introduction to polymer studies in the early 1980s, twodimensional (2D) N M R (88) has continued to surprise and to delight N M R spectroscopists with the range and the depth of its problem-solving ability. This technique has become widely practiced and is commonly being used (89). In this volume Newmark has reviewed some of the standard 2D experiments and compared their performance (54). Brar et al have applied 2D experiments to polyvinyl alcohol) (53) and to acrylonitrile copolymers (52). Chai et al have reported a 2D N M R study of polyurethane dendritic wedges (51). X u et al. have used 2D N M R to assign the N M R spectra of ethylcellulose (65). In their spectral assignments of polypropylene, Segre et al have obtained relevant 2D N M R data (55). 2D N M R has also been used in the papers by Martinez-Richa (59), Sachinvala et al (64), and Yang et al (58). Three-dimensional (3D) N M R is an upcoming area that holds a lot of promise. Peter Rinaldi, who is an acknowledged leader in 2D and 3D N M R , has written a timely and authoritative review in a special Invited Paper (48). In addition, he and his coworkers have used 3D N M R and triple resonance methods to study poly(dimethylsiloxanes) (50), and fluoropolymers (49).

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Hyphenated Techniques

One of the research trends in analytical chemistry is the combining of analytical techniques, and polymer chemistry is no exception. In fact, combined fractionation-NMR (off-line) has been around for many years (90). Recently, many papers have appeared, coupling N M R to SEC and L C , either off-line or on-line. A n off-line S E C - N M R investigation of several copolymers has been reported by Montaudo et al (68). On-line S E C - N M R studies have been made of polymer mixtures by W u and Beshah (67), and of alginates by Neiss and Cheng (69). On-line H P L C - N M R has been used for oligomer analysis by Hiller and Pasch (66). On-line liquid chromatography critical adsorption point ( L C C A P ) N M R has been employed to study tacticity distribution of poly(ethyl methacrylate) by Ute et al (84). In the literature, supercritical fluid chromatography (SFC)-NMR has been engaged for the analysis of plasticizers (91). Off-line capillary electrophoresisN M R has also been reported, and a recent review is available (92).


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Isotopic Labeling

Isotopic labeling is a very useful technique in N M R studies of polymers. For example, C N M R studies of polymers and copolymers prepared using C enriched initiators have been carried out to obtain information about the chemo-, regio-, and stereo-selectivity of radicals derived from such initiators (93-95). In addition, F and P labeling has permitted the studies of chain ends obtained from F a n d ^-containing initiators and chain transfer agents (72,95). C and H labeling has been one of the methods employed to study the reaction mechanism of cationic ring-opening copolymerization of trioxane and dioxolane (73). In the literature, specific C labeling has been used for ZieglerNatta and metallocene catalysis in order to probe reaction mechanism (96). Segre et al have employed C-enriched C O to quench propylene polymerization and to determine the structure of active chain ends (55). Isotopic labeling can facilitate relaxation studies of polymers. In their relaxation studies, Blum and Durairaj have used H labeling on their polyacrylates (70). Luther et al have labeled their polyphosphazenes with N in their work (71). 1 3

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Theoretical Modeling

One of the advantages of N M R in polymer solution studies is the wealth of information available. A N M R spectrum may contain information on polymer microstructure, polymerization mechanism, side reactions, compositional heterogeneity, and (sometimes) molecular weight. Frequently, the challenge is to interpret the spectrum, to extract the relevant information, and to maximize the information content. One way whereby this can be accomplished is through theoretical modeling. This can be carried out, for example, for the polymer structure, polymerization statistics, and reaction kinetics. The use of statistical models to interpret (and to rationalize) N M R tacticity and sequence data is well established (97,98). In this volume the enantiomorphic-site model has been used by Segre et al in their studies of polypropylene at high fields (55). A two-site model has been employed by Shimozawa et al to observe the effects of internal donors in propylene polymerization (56). Other models for polyolefins have been reported in the literature, e.g., the multi-site model (99), the dual catalytic-site/chain-end model (100), the perturbed model (101), the consecutive two-site model (102), the fourcomponent model (103), and the chain end model (104).


7 A recent theoretical development is the use of N M R to study compositional heterogeneity. Two approaches can be used: 1) perturbed Markovian (continuous) model (105), and 2) multi-component (discrete) model (99). Neiss and Cheng have applied the discrete model to the S E C - N M R data of alginates (69). In an earlier work, the N M R data of alginates have also been fitted to a continuous model (106).


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Computer-Assisted Methodologies

Computer methods have often been engaged for polymer microstructural studies (33). A common methodology is to use the computer to fit the observed data to a given theoretical model (model-fitting or analytical approach). Examples are the data treatment given in the papers by Segre et al (55), Shimozawa et al. (56), and Neiss and Cheng (69). A n alternative method is to simulate or to predict the observed data (simulation or synthetic approach). The data may be the N M R spectrum (107), N M R tacticity or sequence intensities (108), or the chemical composition distribution (109). Examples in the literature include polystyrene tacticity (using a statistical model) (110) and low-density polyethylene (using a kinetic model) (111). Molecular modeling and conformational analysis has been used by Martinez-Richa et al. to determine the minimum-energy conformers in polyimides (59). Molecular modeling has also been employed for the conformational analysis of polyisocyanate model compounds (85). A review article on N M R conformational analysis has recently appeared (112). In the identification of unknown polymers, it is often necessary to search an appropriate spectral library. Computer methods have been reported that help in this search (113,114). Many other papers have also reported the use of computers in various contexts, but space limitations preclude a comprehensive coverage here.

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Relaxation Studies

The use of N M R relaxation in polymer solutions is well known (115). This is an excellent technique to study polymer chain dynamics (116), polymer/polymer, polymer/solvent, polymer/additive interactions (117), and phase transitions (118). In this volume, Blum and Durairaj have used H relaxation to probe the dynamics of deuterated polyacrylates in concentrated chloroform solutions (70). Luther et al have carried out N and T relaxation studies to elucidate the interaction between lithium ions and N-labelled polyphosphazenes (71). 2

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8 Baianu and Ozu have used low-field relaxation data (together with highresolution *H and C spectra) to study the gelling mechanism of glucomannans in water (63). l 3


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Other Methods

Because of the need for spectral assignments, the prediction of chemical shifts remains an active area of research. Two popular methods are γ-gauche rotational isomeric state (RIS) model (119) and the empirical additive shift rules (120,121). For example, in their polyester work, Fawcett et al have derived empirical additive shift rules that pertain to their polymeric system (57). Diffusion measurements continue to be a recurring theme in the N M R literature. Quite a few papers have been published on diffusion in polymer solutions, mostly with the pulsed field gradient (PFG) technique (122). Diffusion-ordered spectroscopy (DOSY), a 2D method based on P F G , has been used on several polymer systems (123). A different approach to diffusion measurement has also been reported (124). A n exciting technique is rheo-NMR, being further developed by Callaghan (125). In this way the N M R behavior and rheology of complex fluids can be studied. A n alternative method is the use of N M R imaging to study polymer rheology (126). Another development is nano-NMR, which uses a probe containing a smallvolume sample cell that rotates at - 2 kHz about the magic angle. This technique is suitable for studies of heterogeneous samples as well as for samples that are limited in quantity. This has been successfully applied to carbohydrates (83). A n interesting trend is the increasing use of in situ NMR to study polymerization kinetics, curing reactions, or to determine the comonomer reactivity ratios (127). High-pressure, high resolution H N M R has been employed to study polymer/solvent interactions in poly(l,l-hydroperfluorooctyl acrylate) and its copolymer with styrene (128). l

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Application Areas

In view of its problem solving ability, it is not surprising that liquid-state N M R has been applied to a wide range of polymeric materials. A relatively comprehensive review of the different polymer types has recently appeared (1). A brief survey is given below.


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Addition Polymers

These polymers have been widely studied by N M R . In general, there are several types of information available, depending on the polymer in question, stereochemistry, e.g., homopolymer tacticity regiochemistry, e.g., normal or inverted monomer addition comonomer sequence placement (in copolymers) compositional and tacticity heterogeneity molecular weight effects, e.g., chain end structures in lowmolecular-weight polymers branching and crosslinked structures geometric isomerism, e.g., cis and trans isomers in polydienes Addition polymers reported in this volume include fluoropolymers (49), polypropylene (55,56), polystyrene (66,67), polyacrylates (54,70), styrene-ethyl acrylate copolymer (66), styrene-methyl methacrylate copolymer (67,68), and acrylonitrile copolymers (52). b.

Condensation Polymers

Condensation polymers are easily amenable to N M R analysis. However, the information content is variable, depending on the polymer structures involved. There are several examples of condensation polymers in this volume: i. Polyesters (57) ii. Polyurethanes (51) iii. Polyimides (59) iv. Polysiloxanes (50) v. Phenolic polymers (60) c.

Ring-Opening Polymers

Examples given in this volume are the papers by Yang (on the cationic copolymerization of trioxane and 1,3-dioxepane) (58) and by Luther (on N labelled polyphosphazenes) (71). Poly(ethylene oxide) is also included in the H P L C - N M R studies by Hiller and Pasch (66). l 5

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Natural polymers

The use of N M R for natural polymers is widespread. A large part of the effort has been directed towards proteins and polynucleotides. Two excellent examples are given in two preprints (81,82). Similarly, the polysaccharide area has its share of N M R studies. In this volume, Bush has expounded the origins of the flexibilities of complex polysaccharides (61). Huckerby et al. have carried out a careful structural investigation of keratan sulfates using N M R (62), and


10 Neiss and Cheng have studied the microstructure of alginates and related it to the action of enzymes (69). Baianu and Ozu have examined the gelling mechanism of konjac gum and its interactions with proteins (63). Other studies include bacterial exopolysaccharides (86) and oligosaccharides (83,87).


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Polymer Reactions

Frequently the polymers found in nature or made commercially need some improvements in their end-use properties for specific applications. In such cases, modification reactions can be made on the polymers. A notable case is cellulose, which is insoluble in water and in most organic solvents. Suitable reactions are done industrially to convert it to esters or ethers. Sachinvala et al. have synthesized a number of di- and tri-substituted cellulose ethers and characterized them by N M R (64). X u et al. have used 2D N M R to analyze ethyl cellulose, a commercial polymer (65). Newmark has used 2D N M R to study cellulose acetate butyrate (54). Other uses of N M R to study polymer reactions have been reviewed elsewhere (129).

Solid State N M R 1. General Comments A variety of N M R methods can be used to characterize the structure and dynamics of polymers (both synthetic and naturally occurring) over a wide range of length and time scales. The length scales probed correspond to: 1) the primary chemical structure of the maeromolecular chain (monomer content, sequencing, tacticity, etc.), 2) the secondary structure which is usually a two dimensional ordering such as a hydrogen-bonded sheet, and 3) the tertiary structure such as globular folding in proteins or the three dimensional crystal structure. Beyond these length scales, that are appropriate for individual molecules, are length scales that are characteristic of the morphology and/or phase structure. Characterization of the polymer primary structure is best carried out using solution N M R methods due to the increased spectral specificity of 'solution' N M R methods as compared to solid state N M R methods. 'Solution N M R methods here includes solutions, gels, dispersions, melts, etc. Any method involving dilution, dispersion, increased temperature, etc. that will introduce sufficient motion into the polymer chain such that the unwanted nuclear spin interactions can be averaged to their trace values (zero for dipolar, isotropic chemical shift for the chemical shift anisotropy, scalar coupling for the indirect dipolar interaction, and zero for quadrupolar), on a sufficiently short time scale, 5


11 will advance the ability to observe a 'solution' N M R spectrum. For many naturally occurring polymers and all thermoplastic synthetic polymers, solution N M R methods are the best approach. For a few naturally occurring polymers (45,46) and most thermosetting (43) synthetic polymers, it can be impossible to obtain a 'solution' N M R spectrum without significantly modifying the backbone structure. In these cases, even for the characterization of the primary chemical structure of the molecule, solid-state N M R methods may be required. A classic comparison of the information available from solution and solid state C N M R methods is available (130). For determination of the primary chemical structure in the solid state the primary experiment utilized is the cross-polarization magic angle spinning (CP/MAS) C N M R experiment. This experiment and a variety of other solid state N M R experiments are lucidly described in a book (131). Investigations of the secondary or tertiary structure of polymers cannot be carried out with solution N M R methods because the very act of 'dissolution' destroys these structures. The chain conformation of a polymer that is intimately associated with another material, such as an inclusion complex (44), and the phase structure of a blend (42) are two examples of the importance of longer length scale structures requiring that the structure at all length scales be determined in the solid state. Furthermore, characterization of the molecular dynamics must be carried out in the solid state i f the objective is to understand the dynamic structure in the solid state (47). This information can be related to other relaxation methods such as anelastic and dielectric relaxation to develop an understanding of a variety of properties such as toughness, permeability, secondary/tertiary structure, and structure/property/processing relationships. 1 3


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2. Experimental Techniques Solid state N M R is a vibrant and exciting field where many new techniques appear regularly. A n overview of some selected techniques is given here. a. Techniques for Polymer Structure and Conformation The solid state N M R spectrum tends to have broad lines because of chemical shift anisotropy and dipolar and quadrupolar couplings (11,15,130134). The use of high-power dipolar decoupling, cross polarization (CP) and magic angle spinning (MAS) to produce high resolution C spectra and to cut down on the instrument running time is well known (135). Likewise, the combined rotation and multi-pulse (CRAMPS) experiment can permit *H spectra with narrower linewidths to be obtained (136). Recently, with increasing 1 3


12 spinning rates (up to 50 KHz), M A S alone can sometimes produce relatively narrow lines in the *H solid state spectra (14,137). For these high-resolution solid state spectra, many techniques analogous to those used in solution N M R can be applied. For example, 2D H E T C O R experiments have been achieved using several pulse sequences (138). 2D double quantum correlation N M R (equivalent to 2D inadequate in solution and requiring C-labelled spin pairs) has been found to be a good technique to study chain conformations in the solid state (139). Homonuclear H-*H double quantum M A S experiment has been used to get detailed structural information for several chemical systems (140). In addition, the rotational-echo double resonance (REDOR) is a powerful technique to determine distances between two hetero-nuclei (141). Methods have also been developed that permit the detection of torsional angles (142). 13


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b. Techniques for Polymer Morphology A major application of solid state N M R is the study of polymer morphology. Information potentially available includes the amount and orientation of crystalline phases in semi-crystalline polymers and the domain sizes in phaseseparated polymeric systems. For the deteraiination of crystallinity, a common method is to measure T i relaxation in *H N M R (or H N M R for deuterated polymers). The relaxation data can often be resolved into two (or more) components, which may correspond to magnetization arising from crystalline and amorphous phases (11-15,130-134). The development of the maximum entropy regularization method has permitted more facile and less subjective analysis of the data (143). In optimal cases, multiple components can be identified. A n alternative approach is to determine the crystalline content from the solid state N M R spectra. For example, this can sometimes be done from C N M R spectra with M A S or C P / M A S experiments. Another way to study semicrystalline polymers is X e spectroscopy, whereby the degree of crystallinity, free volume, and the presence of micropores in polymeric materials may be ascertained (144). N M R is particularly suited for the measurement of domain sizes in the range of 5 - 2 0 0 Â (145), which can be probed with a spin diffusion experiment, e.g., Goldman-Shen sequence (146) and dipolar filter pulse sequence (147). The use of multidimensional techniques to study length scales in heterogeneous polymers has been previously reviewed by Spiess (148). 2

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c. Techniques for Polymer Dynamics Among the most popular methods to study polymer dynamics are the


13 relaxation times, T Τ , Τ , and T h> and nuclear Overhauser effects (NOE) (11-15,130-134). T and N O E are sensitive to higher frequency motions (10 10 s), whereas T and T are sensitive to lower frequency motions (10°-10 s). A second group of techniques may be called "lineshape analysis." Simple methods entail the measurements of linewidths or second moments as a function of temperature. More sophisticated methods involve the analysis or the model fitting of spectral lineshapes. A prominent method is I D H lineshape analysis for deuterium-labeled polymers, which is sensitive to motions in the frequency range of 10 -10 s (149). The 2D wideline separation N M R (WISE) experiment permits correlation of the C high resolution spectrum with the wideline *H spectrum, which provides dipolar information (11,150). The *H linewidth is a function of the frequency of the polymer motion relative to the time scale of dipolar couplings. For low-frequency motions (10°-10 s), the 2D H exchange experiments are useful techniques (19). Other exchange experiments are also informative, e.g., the one-dimensional exchange spectroscopy by sideband alternation (ODESSA) (151), time-reversed O D E S S A (152), and centerband-only detection of exchange (CODEX) (153). Many advanced techniques are given in a recent, excellent review by Brown and Spiess (14). 1 ?

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14 11. Mirau, P. A. Solid State NMR of Polymers, R A P R A Report 128, Rapra, Shewsbury, U K . (Rapra Rev. 2001, 11(8), 1). 12. Aliev, A . E.; Law, R. V. Nucl. Magn. Reson. 2001, 30, 214 13. Dybowski, C.; Bai, S. Anal. Chem. 2000, 72, 1. 14. Brown, S. P.; Spiess, H . W . Chem. Rev. 2001, 101, 4125. 15. Solid State NMR of Polymers; Ando I.; Asakura, T. Elsevier, New York, 1998. 16.. Spiess, H. W. AIP Conf. Proc. 2000, 519, 33. 17. Spiess, H . W . Annu. Rep. NMR Spectrosc. 1997, 34, 1. 18. Spiess, H . W . A C S Polym. Prepr. 1997, 38(1), 768. 19. Multidimensional Solid-State NMR and Polymers; Schmidt-Rohr, K.; Spiess, H.W. ; Academic Press, San Diego, 1994. 20. Blumich, B . ; Blumler, P.; Gasper, L . ; Guthausen, Α.; Gobbels, V.; Laukemper-Ostendorf, S.; Unseld, K . ; Zimmer, G . Macromol. Symp. 1999, 141, 83. 21. Horii, F.; Kaji, H . ; Ishida, H . ; Kuwabara, K.; Masuda, K.; Tai, T. J. Mol. Struct. 1998, 441, 303. 22. McBrierty, V . J.; Martin, S. J.; Karasz, F. E. J. Mol. Liq. 1999, 80, 179. 23. Mori, M.; Koenig, J. L . Annu. Rep. NMR Spectrosc. 1997, 34, 231. 24. Whittaker, A . K . Annu. Rep. NMR Spectrosc. 1997, 34, 105. 25. Smirnov, L. P. Vysokomol. Soedin., Ser. A Ser. Β 2000, 42, 1775. 26. Yasunaga, H . ; Kobayashi, M.; Matsukawa, S.; Kurosu, H . ; Ando, I. Annu. Rep. NMR Spectrosc.1997, 34, 39. 27. Matsukawa, S.; Y., H.; Zhao, C.; Kuroki, S.; Kurosu, H . ; Ando, I. Prog. Polym. Sci. 1999, 24, 995. 28. Cohen Addad, J. P. Prog. Nucl. Magn. Reson. Spect. 1993, 25, 1. 29. Preuschen, J.; Rottstegge, J.; Spiess, H . W . Colloids Surf., A 1999, 158, 89. 30. Stilbs, P. in Polymer-Surfactant Systems;M.Dekker; 1998. (Surfactant Sci. Ser. 1998, 77, 239). 31. Blum, F. D . in Colloid-Polym. Interact; Farinato, R. S.; Dubin, P.L., Eds.; pp. 207-223, Wiley, New York, 1999. 32. Ando, I.; Kuroki, S.; Kurosu, H . ; Yamanobe, T. Prog. Nucl. Magn. Reson. Spectrosc. 2001, 39, 79. 33. Cheng, Η. N. Polym. News 2000, 25, 114. 34. Busico, V . ; Cipullo, R. Prog. Polym. Sci. 2001, 26, 443 35. Takeuchi, Y.; Takayama, T. in Chem. Dienes Polyenes; Rappoport, Z., Ed.; Wiley, Chichester, U K , 2000, V o l . 2, pp. 59-196. 36. Demco, D.E.; Blumich, B . Curr. Opin. Solid State Mater. Sci.2001, 5, 195. 37. Watanabe, T. Nucl. Magn. Reson. 2001, 30, 453. 38. Miller, J. B. Prog. Nucl. Magn. Reson. Spectrosc. 1998, 33, 273. 39. Watanabe, T. Nucl. Magn. Reson. 1997, 26, 447. 40. Parker, D . D.; Koenig, J. L. Curr. Trends Polym. Sci. 1996, 1, 65.



15 41. Cheng, Η. Ν.; Early, T. A . Macromol. Symp. 1994, 86, 1. 42. Mirau, P. Α.; Yang, S. ACS Symp. Ser. (this volume), Chap. 2; also, ACS Polym. Prepr. 2001, 42(1), 47. 43. Thakur, K. A. ACS Symp. Ser. (this volume), Chap. 3; also, ACS Polym. Prepr. 2001, 42(1), 57. 44. Tonelli, A . E.; L u , J.; Mirau, P. A. ACS Symp. Ser. (this volume), Chap. 4; also, ACS Polym. Prepr. 2001, 42(1), 53. 45. Tang, S.; Jacob, M. M.; Li, L.; Cholli, A . L..; Kumar, J. ACS Symp. Ser. (this volume), Chap. 5; also, ACS Polym. Prepr. 2001, 42(1), 19. 46. Asakura, T.; Ashida, J.; Yamane, T. ACS Symp. Ser. (this volume), Chap. 6; also, ACS Polym. Prepr. 2001, 42(1), 61. 47. Chujo, R.; Fukutani, K . ; Magoshi, Y. ACS Symp. Ser. (this volume), Chap. 7; also, ACS Polym. Prepr. 2001, 42(1), 29. 48. Rinaldi, P. L. ACS Symp. Ser. (this volume), Chap. 8. 49. Assemat, O.; Rinaldi, P. L . ACS Symp. Ser. (this volume), Chap. 9; also, ACS Polym. Prepr. 2001, 42(1), 9. 50. Chai, M.; Rinaldi, P. L . ; Hu, S. ACS Symp. Ser. (this volume), Chap. 10; also, ACS Polym. Prepr. 2001, 42(1), 15. 51. Chai, M.; Rinaldi, P. L.; Puapaiboon, U.; Taylor, R. T. ACS Symp. Ser. (this volume), Chap. 11; also, ACS Polym. Prepr. 2001, 42(1), 33. 52. Brar, A.S. ACS Symp. Ser. (this volume), Chap. 12; also, ACS Polym. Prepr. 2001, 42(1), 11. 53. Brar, A.S.; Kumar, R.; Yadav, Α.; Kaur, M. ACS Symp. Ser. (this volume), Chap. 13; also, ACS Polym. Prepr. 2001, 42(1), 43. 54. Newmark, R. Α.; Battiste, J. L . ; Koivula, M. N. ACS Symp. Ser. (this volume), Chap. 14; also, ACS Polym. Prepr. 2001, 42(1), 17. 55. Busico, V . ; Mannina, L . ; Segre, A . L . ; Van Axel Castelli, V . ACS Symp. Ser. (this volume), Chap. 15; also, ACS Polym. Prepr. 2001, 42(1), 6. 56. Shimozawa, K . ; Saito, M.; Chujo, R. ACS Symp. Ser. (this volume), Chap. 16; also, ACS Polym. Prepr. 2001, 42(1), 28. 57. Andrews, G.P.; Fawcett, A . H . ; Hania, M . I . M . ACS Symp. Ser. (this volume), Chap. 17; also, ACS Polym. Prepr. 2001, 42(1), 37. 58. Cui, M . - H . , Zhang, Y.; Werner, M.; Yang, N . - L . ; Fenelli, S. P.; Grates, J.A. ACS Symp. Ser. (this volume), Chap. 18; also, ACS Polym. Prepr. 2001, 42(1), 21. 59. Martinez-Richa, Α.; Vera-Graziano, R.; Likhatchev, D. ACS Symp. Ser. (this volume), Chap. 19; also, ACS Polym. Prepr. 2001, 42(1), 13. 60. Sahoo, S. K.; Liu, W.; Samuelson, L.; Kumar, J.; Cholli, A. L. ACS Symp. Ser. (this volume), Chap. 20; also, ACS Polym. Prepr. 2001, 42(1), 35. 61. Bush, C. A. ACS Symp. Ser. (this volume), Chap. 21; also, ACS Polym. Prepr. 2001, 42(1), 62.



16 62. Huckerby, T. Ν.; Brown, G. M.; Lauder, R. M.; Nieduszynski, I. A . ACS Symp: Ser. (this volume), Chap. 22; also, ACS Polym. Prepr. 2001, 42(1), 78. 63. Baianu, I.C.; Ozu, E . M . ACS Symp. Ser. (this volume), Chap. 23; also, ACS Polym. Prepr. 2001, 42(1), 65. 64. Sachinvala, N. D.; Winsor, D . L.; Niemczura, W . P.; Maskos, K . ; Vigo, T. L.; Bertoniere, N. R. ACS Symp. Ser. (this volume), Chap. 24; also, ACS Polym. Prepr. 2001, 42(1), 81. 65 X u , Q.; Brickhouse, M . D . ; Wang, H. ACS Symp. Ser. (this volume), Chap. 25; also, ACS Polym. Prepr. 2001, 42(1), 83. 66. Hiller, W . G.; Pasch, H . ACS Symp. Ser. (this volume), Chap. 26; also, ACS Polym. Prepr. 2001, 42(1), 66. 67. W u , J.; Beshah, K . ACS Symp. Ser. (this volume), Chap. 27; also, ACS Polym. Prepr. 2001, 42(1),23. 68. Montaudo, M.S. ACS Symp. Ser. (this volume), Chap. 28; also, ACS Polym. Prepr. 2001, 42(1), 69. 69 Neiss, T.G.; Cheng, H . N . ACS Symp. Ser. (this volume), Chap. 29; also, ACS Polym. Prepr. 2001, 42(1), 76. 70. Blum, F. D . ; Durairaj, R. B. ACS Symp. Ser. (this volume), Chap. 30; also, ACS Polym. Prepr. 2001, 42(1), 71. 71. Luther, T. Α.; Harrup, M. K.; Stewart, F. F. ACS Symp. Ser. (this volume), Chap. 31; also, ACS Polym. Prepr. 2001, 42(1), 72. 72. Harwood, H . J.; Barkes, B . R.; Medsker, R. ACS Polym. Prepr. 2001, 42(1), 2. 73. Yang, N.-L.; Dunn, P.; Werner, M.; Fenelli, S. P.; Grates, J. A. ACS Polym. Prepr. 2001, 42(1), 4. 74. Grassi, Α.; Trezza, E. ACS Polym. Prepr. 2001, 42(1), 26. 75. Fawcett, A . H . ; Burns, W.; Foster, A . B . ACS Polym. Prepr. 2001, 42(1), 31. 76. Steckle, W . P.; Anglois, D . Α.; Small, J. H . ACS Polym. Prepr. 2001, 42(1), 41. 77. De Angelis, Α. Α.; Segre, A. L.; Capitani, D.; Crescenzi, V . ACS Polym. Prepr. 2001, 42(1), 45. 78. Inglefield, P. T.; Jones, A . A . ; Wen, W . ; Wang, Y. ACS Polym. Prepr., 2001, 42(1), 49. 79. Wutz, C.; Samulski, E. T.; Tanner, M.; Brookhart, M. ACS Polym. Prepr., 2001, 42(1), 51. 80. Davis, R. D.; Mathias, L . J.; Jarrett, Jr.; W . L . ACS Polym. Prepr. 2001, 42(1), 55. 81. Pardi, Α.; Mollova, E.; McCallum, S.; Hanson, P.; Bondensgaard, K . ACS Polym. Prepr. 2001, 42(1), 59. 82. Prestegard, J. H. ACS Polym. Prepr. 2001, 42(1), 60.


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